Reaction product of a polymerized 1, 2-alkylene imine and an epoxy, thioethoxy or hydroxy aromatic compound, each containing an oleophilic group of at least 10 carbon atoms



United States Patent REACTION PRODUCT OF A POLYMERIZED 1,2- ALKYLENE IMINE AND AN EPOXY, THIOETH- OXY OR HYDROXY AROMATIC COMPOUND, EACH CONTAINING AN OLEOPHILIC GROUP OF AT LEAST CARBON ATOMS Henricns G. P. van der Voort, Amsterdam, Netherlands,

assignor to Shell Oil Company, New York, N.Y., a corporation of Delaware No Drawing. Original application Dec. 8, 1960, Ser. No. 74,469, new Patent No. 3,189,546, dated June 15, 1965. Divided and this application Feb. 26, 1965, Ser. No. 435,675

Claims priority, application Netherlands, Feb. 9, 1960,

8 Claims. cl. zen-404.5

This patent application is a division of copending patent application, Serial No. 74,469, filed December 8, 1960, now US. Patent 3,189,546.

The invention relates to a new and novel class of oilsoluble polymers which when added in small amounts to lubricants impart detergent and Wear inhibiting properties thereto.

The novel oil-soluble detergent and wear inhibiting polymers of the present invention are obtained by reacting (1) polymerized 1,2-alkylene imines with (II) a nonpolymerizable oil-soluble polar-containing compound selected from the group consisting of (Ila) expoxy or thioethoxy compounds having an oleophilic group of at least 10 carbon atoms, preferably a C alkyl radical in the molecule or (IIb) a hydroxy aromatic compound containing an oleophilic C preferably C1448 alkyl radical in the molecule.

The polymerized imines are derived from 1,2-alkylene imines having from 2 to 16 carbon atoms and the formula CHz-CHR in which R is H or an alkyl radical.

The polymerized 1,2-alkylene imines (I) are preferably polymerization products of ethylene imine and/or propylene imine, although polymerization products derived from higher C-alkyl ethylene imines the alkyl radical having from 3 to 14 carbon atoms, such as l,2-butyleneimine, C-propyl ethylene imine, C-tetradecyl ethyleneimine and others are also suitable. These polymerized alkylene imines may be prepared in a known manner, e.g.,

by treating the corresponding monomers with small quantities of acid catalysts such as hydrochloric acid, as described in the German patent specification 665,791 or by condensation of alkylene dichlorides with ammonia as described in US. Patent 2,318,730 or by thermal decarboxylation of 2-oxazolidones. The resultant products generally consist of mixtures of polymerization products of varying degrees of polymerization and may contain either branched-chain or straight-chain molecules. The polymerized 1,2-alkylene imines should be oil-soluble and have an average degree of polymerization such that it is within the intrinsic viscosity range from about 0.025 to about 3 when measured in isopropanol at 25 C. Such polyalkylene imines have an average of 1525 imine units in the molecule and are available commercially as 40- 70% water solutions under the trade name Polymin P, which is a to 70% water solution of polyethylene imine. A preferable Polymin P (A) is one containing about 47% by weight of polyethylene imines, about 53% by weight water and 4.76 milligram atoms of basic nitrogen per gram.

Suitable organic compounds (IIa) or (IIb) which are reacted with polymerized 1,2-alky1ene imines to oil-soluble products are as stated (Ila) compounds containing an oleophilic group (alkyl group) having at least 10 Patented Oct. 4, 1966 "ice carbon atoms and an oxirane ring or its thio counterpart. Examples of such compounds include epoxy alkanes such as epoxy dodecane, epoxy tridecane, epoxy tetradecane, epoxy pentadecane, epoxy hexadecane and the like. Particularly suitable are the epoxy alkanes which may be obtained by epoxidiation of olefins having from 14 to 18 carbon atoms. Other examples of suitable epoxy compounds are: (Ha esters of an aliphatic carboxylic acid having 10-30 carbon atoms preferably 12-18 carbon atoms and an epoxy alcohol, particularly esters of an aliphatic carboxylic acid and glycidol, such as glycidyl laurate, glycidyl stearate, thioglycidyl laurate or (I132) ethers containing an epoxy ring, such as epoxy aryl ethers in which the aryl group carries an alkyl group with at least 8 carbon atoms, especially glycidyl-alkyl phenyl ethers, such as glycidyl-C -C alkylphenyl ether. Use may also be made of epoxy or thioepoxy alkyl-alkyl ethers, for instance glycidyl-alkyl ethers such as glycidyllauryl ether or glycidyl stearyl ether, thioglycidyl lauryl ether, glycidyl ether of C1448 alkyl pheno Suitable organic compounds (IIb) are compounds containing a phenolic hydroxyl group, preferably alkyl phenols, particularly C14C13 alkyl phenols, e.g., tetradecyl, hexadecyl, octadecyl phenols, as Well as C C cracked wax olefin phenols.

According to the invention the polymerization products of 1,2-alkylene imines are converted with the organic compounds (II) by contacting the components, preferably in the liquid phase; in a homogeneous medium. The polymerized 1,2-alkylene imine is generally employed as a solution in an organic solvent, which if desired, may also contain water. Suitable solvents are in particular alcohols having from 1 to 10 carbon atoms, e.g. methanol, ethanol, isopropanol, the butanols, pentanols, and the higher alcohols, for example isooctanol and isononanol and ether alcohols, such as butyl carbitol, and also mixtures of these alcohols with water and/or hydrocarbon, for example gasoline fractions or benzenoid hydrocarbons. The organic compounds (II) are added as such to the solution of the polymerized 1,2-alkylene imines although if desired they may also be used as a solution in an organic solvent. Suitable organic solvents for this purpose are aliphatic alcohols having from 1 to 10 carbon atoms as defined hereinbefore, hydrocarbons, e.g. gasoline fraction and benzenoid hydrocarbons, and mixtures of these organic solvents.

In an advantageous embodiment of the invention an aqueous isopropanol solution of a polymerized 1,2-alkylene imine is contacted with one or more of the suitable organic compounds, after which the solvents are removed by distillation, if desired under reduced pressure. It is also possible to remove the solvents by distillation with steam of C. or superheated steam, for example steam of C., if desired also under reduced pressure. It is preferred to add to the mixture a light petroleum oil, for example a mineral lubricating oil fraction of low viscosity, before the solvents are removed so that after the removal of the solvents a concentrate is obtained which is suitable for addition as such to a lubricating oil. No operations such as centrifuging or filtering are required. All that is required to obtain a product is clear and entirely soluble in lubricating oil is the removal of the solvents by distillation.

The reaction is generally carried out at temperatures in the range of from 20 C. to 130 C., although higher or lower temperatures are also possible. The reactants are generall reacted in such quantities that an excess of polymerized 1,2-alkylene imine is used per gram-equivalent of the organic compound, viz. more than 1 gramatom of nitrogen per oxirane ring when use is made of a compound containing an oxirane ring, or per double bond when use is made of a compound containing a double bond activated by an esterified carboxyl group, or per hydroxyl group when a compound containing a phenolic hydroxyl group is employed. The excess may be, for example, 25 to 100%, but the use of an equivalent or smaller quantity of polyalkylene imine is not excluded.

The following examples illustrate the present invention. By basic nitrogen in the following examples is meant the base which can be titrated with mineral acid.

EXAMPLE I The starting material was polymerized ethylene imine "Polymin P (a commercial product containing about 47% by weight of polyethylene imines, about 53% by weight of water and 4.76 milligram-atoms of basic nitrogen per gram) from which the water had been removed after addition of ethanol and benzene by azeotropic distillation. A quantity of 19.97 parts by Weight of the water-free product containing an over-all quantity of 199.7 milligram-atoms of basic nitrogen was dissolved in 120 parts by weight of a 1:1 ethanol-benzene mixture. A quantity of 31.2 parts by weight of epoxy dodecane (prepared by expoxidizing dodecane-l) was added to this solution. The mixture contained 0.85 gram-atoms of epoxyoxygen per gram atom of basic nitrogen. The mixture was then boiled under reflux over a steam bath for 20 hours. A quantity of 213.3 parts by weight of an extracted Venezuelan parafiinic lubricating oil having a viscosity of 24 cs. at 100 F. was subsequently added, after which the solvents were removed by distillation with heated steam of 130 C. A quantity of 263.5 parts by weight of concentrate in the said oil was obtained which contained 19% by weight of conversion product and in which per gram 0.85 milliquivalent of basic nitrogen was present.

EXAMPLE II The starting material was the glycidyl ester prepared from a mixture of C branched aliphatic carboxylic acids obtained from C C olefins by adding thereto by means of an addition reaction carbon monoxide and water in the presence of boron trifluoride and phosphoric acid as catalysts. 25.1 parts by weight of this ester (69.1 milligram-atoms of epoxy-oxygen) were dissolved in 50 parts by weight of isopropanol, after which the resultant solution was added to a mixture of 19.65 parts by weight of aqueous Polymin P (commercial product containing approximately 53% by weight of water) and 34.6 parts by weight of isopropanol. The resultant homogeneous mixture containing 0.75 gram-atoms of epoxy oxygen per gram atom of basic nitrogen was then boiled for 5 minutes, after which a quantity of 51.7 parts by weight of an extracted Venezuelan paraflinic lubricating oil having a viscosity of 24 cs. at 100 F. was added and the solvents were removed under reduced pressure. The distillation residue (86.2 parts by weight) was a clear concentrate in the said oil, which concentrate contained 39.8% by weight of conversion product. 1.86 milliequivalent of basic nitrogen was present per gram of concentrate.

EXAMPLE III The sodium salt was prepared from C -C alkyl phenols obtained by alkylating phenol with a mixture of The glycidyl ether of C -C alkyl phenol was prepared from the sodium salt by means of epichlorohydrin. A quantity of 233.5 parts by weight of Polymin P (approximately 53% by weight of water) was diluted with 700 parts by weight of isopropanol. A quantity of 300 parts by weight of the said glycidyl ether was added to this solution of Polymin P containing 110 milliequivalents of basic nitrogen. The resultant mixture containing per gram-atom of basic nitrogen 0.625 gramatoms of epoxy-oxygen was boiled with stirring for half an hour. The solvents were then removed by distillation under reduced pressure, a quantity of 861.7 parts by weight of an extracted paraflinic mineral lubricating oil having a viscosity of 24 cs. at 100 F. being simultaneously added.

4. In this way a quantity of 1277 parts by weight of a 32.1% concentrate of the conversion product was obtained, which concentrate 0.953 milliequivalent of basic nitrogen per gram.

EXAMPLE IV 377.5 parts by Weight of Polymin P (water content approximately 5 3% by weight) were diluted with 700 parts by weight of isopropyl alcohol. A mixture consisting of 343.5 parts by weight of lauryl glycidyl ether (commercial product) with an epoxy-oxygen content of 3.50 milligram-atoms per gram and of 100 parts by weight of isopropanol was then added. The resultant homogeneous solution containing 0.67 gram-atoms of epoxy oxygen per gram-atom of nitrogen was boiled for half an hour. The solvents were distilled off under reduced pressure, a quantity of 1501.5 parts by weight of extracted Venezuelan paraflinic mineral lubricating oil having a viscosity of 24 cs. at 100 F. being simultaneously added. The residue (2020 parts by weight) was a 25.7% concentrate of the conversion product in the said oil and contained 0.99 milliequivalents of basic nitrogen per gram.

EXAMPLE V The starting material was C -C alkyl phenol obtained by alkylating phenol with C 43 olefins and distillation of the alkylation product. The alkyl phenol contained per gram 3.11 mg. eq. OH. A quantity of 213 parts by weight of Polymin P (1015 mg. eq. of basic nitrogen, about 53% by weight of water) was dissolved with stirring in 1000 parts by weight of isopropanol. A quantity of 238 parts by weight of C -C alkyl phenol was added to this solution while stirring was continued. After boiling the mixture for half an hour a quantity of 518 parts by weight of the mineral oil described in the previous examples was added. The solvents were then removed by distillation under reduced pressure at a bath temperature of C. A quantity of 862 parts by weight of residue containing 39.2% by weight of conversion product was obtained. The basic nitrogen content was 1.16 mg. eq. per gram.

EXAMPLE VI The starting materials'were technical alkyl phenols obtained by alkylation of phenol with C -C olefins. In the same manner as described in Example V a quantity of 1406 parts by weightof a 39.5% by weight of concentrate containing 39.5 by weight of conversion product and having a basic nitrogen content of 1.18 mg. eq. per gram was obtained from a quantity of 347 parts by weight of Polymin P (1650 mg. eq. of basic nitrogen, approximately 53% by weight of water). A quantity of 390 parts by weight of technical alkyl phenol (2.09 mg. eq. of

OH per gram) and 849 parts by weight of the mineral lubricating oil referred to in the previous examples in 1000 parts by weight of isopropanol as solvent.

The products obtained according to the invention are suitable as additives to lubricating oils of various types.

Such mineral lubricating oils are of diverse viscosity range Gr. API, 60/60 F. 32 Flash, F. 370 Viscosity index (Dean and Davis) 93 Viscosity, SUS at F. 103

The products may be added as such to the lubricant or in the form of a concentrate thereof obtained by adding a small quantity of a lubricating oil before removing the solvents from the reaction mixture.

The quantity of the products of the invention incorporated into lubricants may vary within wide limits. In general the desired improvement is already obtained when the quantity incorporated varies between 0.05 and 5%, particularly between 0.1 and 1%, based on the finished lubricant. In special cases, however, quantities even greater than the said quantities may be added, for example in the case of diesel engines in which use is made of fuel having a high sulfur content.

In order to demonstrate the utility and improved properties of compositions of the present invention the compositions identified in Tables I, H and III were tested for the oxidation stability and extreme pressure and antiwear properties under the following conditions.

Engine tests The engine tests were carried out in a C.F.R. gasoline engine to determine the anti-wear properties, in a Petter gasoline engine to determine the anti-sludge properties, and in a Caterpillar diesel engine to determine the detergent properties.

C.F.R. gasoline engine Water-cooled single-cylinder, four-stroke engine. The test lasted 45 hours. The fuel was a gasoline having a sulfur content of 0.06% by weight and contained 0.7 ml. TEL per US. gallon. Cylinder cooling water temperature was 40 C.

Petter gasoline engine Water-cooled single-cylinder, four-stroke engine. The test lasted 28 hours. The fuel was a motor gasoline having 1.5 ml. TEL per US. gallon and a sulfur content of 0.07% by weight. The cylinder cooling water temperature was about 500 C.

Caterpillar Water-cooled single-cylinder, four-stroke engine. The test lasted 48 hours. The fuel was a gas oil having a sulfur content of 0.9% by weight. The cooling water temperature was about 80 C. The engine power was 18 HR; bore 5%"; stroke 8"; swept volume 3.4 liters.

The products according to the invention were all tested in the form of solutions in an extruded Venezuelan paraffinic mineral lubricating oil having a viscosity of 114 cs. at 100 R, which lubricating oil in most cases also contained an ash-free lubricating oil additive having detergent properties. The additives according to the invention were added in the form of a concentrate to the mineral lubricating oil and these concentrates had been added according to the examples. The tests are assembled in the following Tables IIII. Table I shows the anti-wear properties imparted by the products according to the invention to the mineral lubricating oil. Table II shows the anti-sludge properties and Table III shows the detergent properties imparted to the lubricating oil.

1 Copolymer of stcaryhnethacrylate/lauryl methacrylate/hydroxyetbyl methacrylate (5:5:2).

Table Il.Petter sludge tests Ash-free additive 1 Sludge- Additive of the invention with detergent rating (concentrate) effect 0 is clean) 1.118% by weight of additive of Example 2% by weight.-." 8. 0 by weight of additive of Example 1.7% by weight 7. 6 0.23% by weight of additive of Example do 7. 7 by weight of additive of Example 2% by weight. 7. 7

None do 6. 5 Dn None 4. 4

1 Note Table I.

Table II1.Caterpillar piston fouling tests Ash-free additive 1 Piston Additive of the invention with detergent Foul ng (concentrate) effect (10 is clean) 0.9%? by weight of additive of Example 1.7% by weight 8. 8

I 0.82% by weight of additive of Example do 9. 2 None do 7. 8 D0 None 4. 5

1 Note Table I.

The additives of this invention are also suitable incorporated into synthetic lubricating oils as well as into lubricating oils containing fatty oils. The products may also be worked up in lubricating greases. The present products are also suitable for being added to liquid fuels such as gasoline, kerosene, gas oil and residual fuels.

In their use the present products may also be combined with other additives, such as anti-oxidants, detergent dopes, viscosity-index improvers, corrosion inhibitors, antifoaming agents, pour-point depressants, extreme-pressure and oiliness agents and other materials generally added to lubricants, fuels and greases.

I claim as my invention:

1. An oil-soluble reaction product obtained by reacting at between 20 C. and C. a polymerized 1,2- alkylene imine containing an average of 1525 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms with an oil-soluble polar-containing compound selected from the group consisting of and epoxy alkane having from 14 to 18 carbon atoms, and thioepoxy alkane having from 14 to 18 carbon atoms in the molecule, esters of glycidol and alkanoic acids having from 10 to 30 carbon atoms, glycidyl ethers of an alcohol selected from the group consisting of alkyl phenol and alkanol each having from 14 to 18 carbon atoms and C1448 alkyl phenols, the imine being present in the amount of 1.25 to 2 gram-equivalents per gram-equivalent of the oil-soluble polar-containing compound.

2. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. a polymerized 1,2- alkylene imine containing an average of 15-25 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms with an oil-soluble epoxy alkane having from 14 to 18 carbon atoms in the molecule, the imine being present in the amount of 1.25-2 gram-equivalents per gram-equivalent of the oil-soluble epoxy alkanol.

3. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. of a polymerized 1,2- alkylene imine containing an average of 15-25 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms with an oil-soluble ester of glycidol and an alkanoic acid having from 10 to 30 carbon atoms in the molecule, the imine being present in the amount of 1.25-2 gram-equivalents per gram-equivalent of the oil-soluble ester.

4. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. a polymerized 1,2- alkylene imine containing an average of 15-25 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms with an oil-soluble glycidyl ether of C1448 alkyl phenol, the imine being present in the amount of 1.25-2 gram-equivalents,

per gram-equivalent of the glycidyl ether compound.

5. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. a polymerized ethylene imine containing an average of 1525 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms and epoxydodecane, the imine being present in the amount of 125-2 gram-equivalents per gram-equivalent of epoxydodecane.

6. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. a polymerized ethylene imine containing an average of 15-25 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms and glycidyl ester of an alkanoic acid having from 14 to 18 carbon atoms in the molecule, the imine being present in the amount of -2 gram-equivalents per gram-equivalent of glycidyl ester compound.

7. An oil-soluble reaction product obtained by reacting at between 20 C. and C. a polymerized ethylene imine containing an average of 15-25. imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms and glycidyl decylether, the imine being present in the amount of 1.25-2 gram-equivalents per gram-equivalent of glycidyl decyl ether.

8. An oil-soluble reaction product obtained by reacting at between 20 C. and 130 C. a polymerized ethylene imine containing an average of 15-25 imine units in the molecule and each alkylene radical in the imine unit having from 2 to 16 carbon atoms and C1448 alkyl phenol, the imine being present in the amount of 1.25-2 gram-equivalents per gram-equivalent of C1445 alkyl phenol.

No references cited.

CHARLES B. PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner. 

1. AN OIL-SOLUBLE REACTION PRODUCT OBTAINED BY REACTING AT BETWEEN 20*C. AND 130*C. A POLYMERIZED 1,2ALKYLENE IMINE CONTAINING AN AVERAGE OF 15-25 IMINE UNITS IN THE MOLECULE AND EACH ALKYLENE RADICAL IN THE IMINE UNIT HAVING FROM 2 TO 16 CARBON ATOMS WITH AN OIL-SOLUBLE POLAR-CONTAINING COMPOUND SELECTED FROM THE GROUP CONSISTING OF AND EPOXY ALKANE HAVING FROM 14 TO 18 CARBON ATOMS, AND THIOEPOXY ALKANE HAVING FROM 14 TO 18 CARBON ATOMS IN THE MOLECULE, ESTERS OF GLYCIDOL AND ALKANOIC ACIDS HAVING FROM 10 TO 30 CARBON ATOMS, GLYCIDYL ETHERS OF AN ALCOHOL SELECTED FROM THE GROU CONSISTING OF ALKYL PHENOL AND ALKANOL EACH HAVING FROM 14 TO 18 CARBON ATONS C14-18 ALKYL PHENOLS, THE IMINE BEING PRESENT IN THE AMOUNT OF 1.25 TO 2 GRAM-EQUIVALENTS PER GRAM-EQUIVALENT OF THE OIL-SOLUBLE POLAR-CONTAINING COMPOUND. 